Hair dyes based on diamino-nitro-benzene compounds

ABSTRACT

A hair dye preparation contains diamino-nitrobenzene compounds as a direct hair dye or contains diamino-nitrobenzene compounds as coupling components in combination with developing components for oxidation dyestuffs. A process for dyeing human hair comprises applying one of these preparations to the hair.

United States Patent Saygin Sept. 23, 1975 [5 HAIR DYES BASED ON 3,506,389 4/1970 Charle 6111]. 8/11 DIAMINO NITRO BENZENE COMPOUNDS 3,563,684 2/1971 Charle'et a1. 8/10.2

3,591,638 7 1971 HillZISZ 8/102 Inventor: Ferd! yg Dusseldorf, G y 3,617,167 11/1971 Berth et 211..... 13/102 [73] Assignee: Therachemie Chemisch gf 'I Therapeutische Gesellschaft m b H 6 W555? et a l 1 3,712.158 1/1973 Kalop1ss1s et a1. 8/10.2 Dusseldorf, Germany 3,820,948 6/1974 Berth 8/11 Filed: Feb. 28, 1973 Appl. No.: 336,696

Related US. Application Data Division of Ser. No. 272,383, July 17, 1972, abandoned.

Foreign Application Priority Data Oct. 4, 1971 Germany 2149467 Feb. 18, 1972 Germany 2207683 U.S. Cl. 8/10; 8/10.1; 8/10f2;

Int. CIF... A61K 7/12; A61K 7/13; D061 3/00; D06P 5/00; D06? 1/32; D06P 3/06 Field of Search 8/10, 10.2, 10.1, 11; 260/562 R, 465 D, 465 B, 471 R, 470, 465.2, 465.4, 558 A, 558 P References Cited UNITED STATES PATENTS 8/1963 Kaiser et a1 8/10,2

FOREIGN PATENTS OR APPLICATIONS A hair dye preparation contains diamino-nitrobenzene compounds as a direct hair dye or contains diaminonitrobenzene compounds as coupling components in combination withvdeveloping components for oxidation dyestuffs. A process for dyeing human hair comprises applying one of these preparations to the hair.

12 Claims, No Drawings Maul HAIR DYES BASED ON DIAMINQ-NITRO-BENZENE COMPOUNDS This is a division of Ser. No. 272,383 filed July 17, 1972, now abandoned.

PRIOR ART OBJECTS OF THE INVENTION It is an object of the present invention to provide an aqueous hair dye preparation containing a diaminonitro-benzene compound which acts as a direct dye or which acts as a coupling component along with a dev'eloper component in an oxidation dye-stuffs combination.

It is another object of the present invention to provide a compound of he formulae selected from the group consisting of wherein X is an electrophilic substituent and A is a member selected from the group consisting of alkyl of 1 to carbon atoms, hydroxyalkyl of l to 10 carbon atoms, N,Ndialkyl-amino-alkyl of 3 to 18 carbon atoms, alkanoyl of 2 to 10 carbon atoms, substituted alkanoyl of 2 to 10 carbon atoms with a substituent selected from the group consisting of nitro, phenyl, halo, cyano, carboxyl and sulfo, acyl of aromatic hydrocarbon carboxylic acids having 7 to carbon atoms, sub stituted acyl of aromatic hydrocarbon carboxylic acids having from 7 to 15 carbon atoms with a substituent selected from the group consisting of lower alkyl, nitro,

halo, cyano, carboxyl and sulfo, and the activated methylene group -COCH X, in which X is an electrophilic substituent.

It is a further object of the present invention to provide a process for dyeing hyman hair which comprises applying to the hair an aqueous hair dye preparation containing a diamino-nitro-benzene compound which acts as a direct dye or which acts as a coupling componentalongwith a developer componentin an oxidation dyestuffs combination. 1 a V Other and further objects of the present invention will become apparent asthe description thereof proceeds.

DESCRIPTION OF THE INVENTION The present invention provides a compound of the formulae selected from the group consisting of wherein X is an electrophilic substituent and A is a member selected from the group consisting of alkyl of l to 10 carbon atoms, hydroxyalkyl of l to 10 carbon atoms, N,N-dialkyl-amino-alkyl of 3 to 18 carbon atoms, alkanoyl of 2 to 10 carbon atoms, substituted alkanoyl of 2 to 10 carbon atoms with a substituent selected from the group consisting of nitro, phenyl, halo, cyano, carboxyl and sulfo, acyl of aromatic hydrocarbon carboxylic acids having 7 to 15 carbon atoms, substituted acyl of aromatic hydrocarbon carboxylic acids having from 7 to 15 carbon atoms with a substituent selected from the group consisting of lower alkyl, nitro, halo, cyano, carboxyl and sulfo, and the activated methylene group COCI-I X, in which X is an electrophilic substituent.

The present invention also provides an aqueous preparation for the direct dyeing of human hair consisting essentially of 1. from 0.1% to 5% by weight of a diamino-nitrobenzene compound of the formula selected from the group consisting of m-cc-ca x' in which X and X are each and electrophilic substituent and A' is a member selected from the group consisting of hydrogen, alkyl of 1 to 10 carbon atoms, hydroxyalkyl of l to 10 carbon atoms, N,N-dia1kyaminoalkyl of 3 to 18 carbon atoms, alkanoyl of 2 to 10 carbon atoms, substituted alkanoyl of 2 to 10 carbon atoms with a substituent selected from the group consisting of nitro, phenyl, halo, cyano, carboxyl and sulfo, acyl of aromatic hydrocarbon carboxylic acids having 7 to 15 carbon atoms, substituted'acyl of aromatic hydrocarbon carboxylic acid having from 7 to 15 carbon atoms with a substituent selected from the group consisting of lower alkyl, nitro, halo, cyano, carboxyl and sulfo; and in which A is selected from the group consisting of A' and the activated methylene group CO CH X, in which X is an electrophilic substituent with the proviso that whenever A is hydrogen, then X is not acetyl;

2. from to 30% by weight of a surfactant; (3) I from 0% to 25% by weight of thickeners; and (4) from 40% to 999% by weight of water.

The present invention is further directed to a process for the direct dyeing of human hair consisting essentially of applying to said hair at temperatures ranging substantially from 15 to 40C for a time sufficient to affect dyeing, an effective amount of an aqueous preparation consisting essentially of l from 0.1% to by weight of a diamino-nitrobenzene compound of the formula selected from the group consisting of x-cii -co-m H and in which X and X are each in electrophilic substituent and A is a member selected from the group consisting of hydrogen, alkyl of 1 to carbon atoms, hydroxyalkyl of l to 10 carbon atoms, N,N-dialkyl-aminoalkyl of 3 to 18 carbon atoms, alkanoyl of 2 to 10 carbon atoms, substituted alkanoyl of 2 to 10 carbon atoms with a substituent selected from the group consisting of nitro, phenyl, cyano, carboxyl and sulfo, acyl of aromatic hydrocarbon carboxylic acids having 7 to carbon atoms, substituted acyl of aromatic hydrocarbon carboxylic acids having from 7 to 15 carbon atoms with a substituent selected from the group consisting of lower alkyl, nitro, halo, cyano, carboxyl and sulfo; and

-co-cs -x' in which A is selected from the group consisting of A and the activated methylene group COCH X, in which X is an electrophilic substituent; (2) from 0% to 30% by weight of a surfactant; 3) from 0% to 25% by weight of thickeners; and (4) from 40% to 99.9% by weight of water.

The present invention further provides an aqueous preparation for the dyeing of human hair consisting essentially of (1) from 0.1% to 5% by weight of an oxidation dyestuffs combination of a developer component, and a coupling component in substantially equimolar amounts, said coupling component consisting essentially of a diamino-nitrobenzene compound of the formula selected from the group consisting of NHA -CO- CH -X and x-cn -co-im H carbon atoms, alkanoyl of 2 to 10 carbon atoms, substituted alkanoyl of 2 to 10 carbon atoms with a substituent selected from the group consisting of nitro, phenyl, halo, cyano, carboxyl and sulfo, acyl of aromatic hydrocarbon carboxylic acids having 7 to 15 carbon atoms, substituted acyl of aromatic hydrocarbon carboxylic acids having from 7 to 15 carbon atoms with a substituent selected from the group consisting of lower alkyl, nitro, halo, cyano, carboxyl and sulfo, and the activated methylene group COCH X, in which X is an electrophilic substituent; (2) from 0% to 30% by weight of a surfactant; (3) from 0% to 25% by weight of thickeners; and (4) from 40% to 99.9% by weight of water.

7 The present invention is still further directed to a process for the dyeing of human hair consisting essentially of applying to said hair at temperatures ranging substantially from 15 to 40C for a time sufficient to affect dyeing, an effective amount of an aqueous preparation for the dyeing of human hair consisting essentially of (1) from 0.1% to 5% by weight of an oxidation dyestuffs combination of a developer component, and a coupling component in substantially equimolar amounts, said coupling component consisting essentially of a diamino-nitrobenzene compound of the formula selected from the group consisting of X-CHZ-CO- in which X is an electrophilic substituent and A is a member selected from the group consisting of hydrogen, alkyl of 1 to 10 carbon atoms, hydroxyalkyl of 1 to 10 carbon atoms; N,N-dialkyl-aminoalkyl of 3 to 18 carbon atoms, alkanoyl of 2 to 10 carbon atoms, substituted alkanoyl of 2 to 10 carbon atoms with a substituent selected from the group consisting of nitro, phenyl, halo, cyano, carboxyl -and sulfo, acyl of aromatic hydrocarbon carboxylic acids having 7 to 15 carbon atoms, substituted acyl of aromatic hydrocarbon carboxylic acids having from 7 to 15 carbon atoms with a substituent selected from the group consisting of lower alkyl, nitro, halo, cyano, carboxyl and sulfo, and the activated methylene group COCH X, in which X is an electrophilic substituent; (2) from 0% to 30% by weight of a surfactant; (3) from 0% to 25% by weight of thickeners; and (4) from 40% to 99.9% by weight of Water.

As electrophilic substituents X, the radicals containing a carbonyl, such as carboxyl, alkoxycarbonyl, and acyl, or a nitrile, or carbonyl containing radicals further substituted with halogen, the sulfo group and the nitro group, are considered. X is preferably a nitrile, acyl, or alkoxycarbonyl group.

The acyl substituent can be derived from aliphatic, cycloaliphatic, heterocyclic or aromatic carboxylic acids and can themselves be substituted. Suitable examples of acyl groups include alkanoyl of 2 to 10 carbon atoms and their nitro, phenyl, halo, cyano, carboxyl and sulfo substituted derivatives, such as acetyl, butyryl, trifluoroacetyl, phenylacetyl, aromatic hydrocarbon carboxylic acids having 7 to 15 carbon atoms and their alkyl, nitro, halo, cyano, carboxyl and sulfo substituted derivatives, such as benzoyl, nitrobenzoyl, chlorobenzoyl, phthaloyl, B-naphthoyl, cycloalkylcarbonyl of 6 to 10 carbon atoms, such as cyclohexylcarbonyl, furoyl, and thenoyl. The alko'xycarbonyl groups represented by X may also be comprised by aromatic or cycloaliphatic radicals, usually alkyl of l to 10 carbon atoms; but also cycloalkyl of 6 to 10 carbon atoms and phenylalkyl of 7 to 16 carbon atoms; for example, they may be derived from benzyl alcohol or cyclohexyl alcohol.

For the reasons for greater availability of the starting material, it is preferable that the acyl substituent be derived from lower aliphatic carboxylic acids with 2 to 4 carbon atoms or'from mononuclear aromatic carboxylic acids. The alkoxycarbonyl residues may be derived from lower aliphatic alcohols with l to 4 carbon atoms.

In addition to A being the activated methylene group CO-CH -X, A could be any one of the above acyls or alkyl and hydroxyalkyl of l to 10 carbon atoms and N,N-diall ylaminoalkyl of 3 to 18 carbon atoms optionally present in the hair dyes of the invention may be present in an arbitrary manner. It is preferable, however, for the above named reasons, that they are short-chained. The alakyl or alkylol radicals preferably have 2 to 4 carbon atoms. The N,N-dialkylaminoalkyl residues are preferably derived from terminal alkyl amines of 2 to 12 carbon atoms, substituted by methyl and/or ethyl groups, for example dimethylaminopropyl, diethylaminohexyl, methylethylaminododecyl.

Of the compounds, falling under the general formula, the following are preferred: l,3-diamino-4-nitrobenzene derivatives of the formula in which X and A' have the same meanings as defined above; and l,4-diamino-nitrobenzene derivatives of the formula mi-co-cn -x l-Trifluoro-aceto-acetylaminio-3-amino-4-nitrobenzene, l-(2-I-Iydroxy-ethylamino)-3-cyanoacetylamino- 4-nitrobenzene,

l-Amino-2-nitro4-w-cyanoacetylamino-benzene 1-Amino-2-nitro-4-co-benzoyl-acetylamino-benzene,

l ,4-Dicyanoacetyl-amino-2nitrobenzene, lAmino-Z- nitro-4-w-ethoxycarbonyl-acetylamino-benzene, l,4- Bis-( w-ethoxycarbonyl-acetylamino)-2-nitrobenzene, l-Amino-2nitro-4-w-benzoxycarbonyl-acetyl-aminobenzene, l-Amino-2-nitro-4-( p-nitrobenzoylacetylamino )-benzene, l'Amino-2-nitro-4- acetoacetylamino-benzene, l-Amino-2-nitro-4- nitroacetoacetylamino-benzene,

1 -Amino-2'nitro 4 trifluoroacetoacetylamino-benzene,

l-Amino-2-nitro-4-m-butyryl-acetylamino-benzene, l-Amino-2-nitro-4-m-( ,B-Naphthoylacetylamino )-benzene,

l'Amino-2-nitro-4-cyclohexylcarbonyl-acetylaminobenzene,

1 -Amino-2-nitro-4-Furoylacetylamino'benzene,

1-Amino-2-nitro-4-Thenoylacetylamino-benzene,

l ,4-Bis-( w-butoxycarbonyl-acetylamino )-benzene,

l ,4-Bis-( w-cyclohexyloxycarbonyl-acetylamino )-benzene.

The hair dyes of the present invention can be prepared by reacting a 1,3-diamino-4-nitrobenzene or a l,4-diamino-nitro-benzene or their derivatives, substituted at an N-atom by the substituents named in the above formulas, with a suitably substitued acetyl chlo ride or acetic acid ester, such as with cyanoacetic acid ethyl ester or cyanoacetyl chloride, malonic acid dialkyl ester or malonic acid monoalkyl ester chloride, ace toacetic acid ethyl ester, benzoylacetic acid methyl ester or benzoylacetyl chloride.

The reaction of l,3-diamino-4-nitrobenzene or 1,4- diamino-nitrobenzene with substituted acetic acid esters, always results in derivatives having a mono substituted nitrogen, independent of the quantitative proportions of the reactions and the other reaction conditions.

The reaction to place a substituent on both amino groups takes place only if the reaction is carried out with substituted acetyl chloride in the presence of nonpolar solvents, such as benzene or hydrocarbons. However the reaction with substituted acetyl chloride in the presence of polar solvents, such as tetrahydrofuran or chlorobenzene, always results in derivatives, having one monosubstitued nitrogen independent of the quantitative proportions of the reactants.

In the case of the reaction with substituted acetic acid esters, the reaction may be carried out in the presence of solvents, whose polarity has no influence on the course of the reaction.

If acid chlorides are a reactant, it is preferable to add to the reaction mixture and acid acceptor, for example and amine, preferably a lower alkylamine or lower alkylolanine such as triethylamine.

The synthesis reaction is generally carried out at reflux temperatures, and in many cases can be followed by a progressive precipitation of the reaction product. The reaction time required is generally 3 to 5 hours. The reaction products may optionally be purified by recrystallization from polar solvents.

The hair dyes of the present invention may be used as direct dyes, with the exception of those derivatives of l,3-diamino4-nitrobenzene which are substituted on both amino groups by the methylene active grouping COCI-l -X. In these direct dyes the member A' 7 excludes this methylene active grouping. All of these dyes are distinguished by their affinity to hair and by their ability to produce clear yellow dyeings of the hair.

A second important utility of the novel hair dyes is in their use as color coupling components for yellowdevelopers in oxidation hair dyes with conventional developers. The attainable shades can be varied by the developer components and the intensity of color produced by oxidation can be varied over a range of different tints from yellow to brown.

The hair dyes, according to the invention, are preferably used in about equal molar amounts with respect to the applied developers. However it is acceptable if the color coupling component is present in an amount greater than the equimolar quantity or less than the equimolar quantity.

Both the color coupling components and the developers may be mixtures of the respective compounds.

Examples of suitable developing agents include aromatic, bi-or polyfunctional amines having at least one primary amino group and another functional group in para-position, or else a 4-amino-pyrazolone.

Preferred 4aminopyrazolones are compounds of the generic formula (1) wherein R and R are hydrogen or an organic radical having 1 to carbon atoms.

The organic radical R can be an alkyl having 1 to 10 carbon atoms, an aryl, such as phenyl, hydroxyphenyl, sulfonylphenyl, sulfonamidophenyl, aminophenyl, lower alkylolphenyl, lower alkyl-phenyl, lower alkylaminophenyl and di-lower alkylaminophenyl where the alkyls and alkylols have 1 to 4 carbon atoms, or a heterocyclic radical, such as the pyridyl. Functional groups may be present, particularly on the aryl, as indicated above, such as OH, NH Nl-lCl-l N(CH or halogen atoms, i.e., fluorine, iodine, bromine, and particularly chlorine. Furthermore, the following groups may be present as organic radicals: COOH, COOR', CONH CONHR, CONRR, wherein R and R" are alkyl or hydroxyalkyl having 1 to 4 carbon atoms.

The organic radical R can be an alkyl having 1 to 10 carbons, an aryl, such as those mentioned above for R or a heterocycylic radical, such as the pyridyl. Functional groups may be present. Particularly, hydrocarbon radicals having 1 to 10 carbons are applicable containing as functional groups OH, NH COOH, CONH SO H and SO NH As aromatic radical, a phenyl is especially applicable. it may be substituted with alkyl or hydroxyalkyl groups having 1 to 4 carbons or other substituents, such as halogen, preferably Cl, NH OH, COOH, CONH CONHR, CONRR, SO H and SO NH It frequently is opportune to employ the 4- aminopyrazolones in the form of their water-soluble acid addition salts, such as the hydrochloride, sulfate or oxalate, because the resistance to atmospheric air is increased.

v 8 4-Aminopyrazolones which are suitable in the process of the invention as formula (1) are as follows:

1 -ethyl-4-aminopyrazolone 1-n-hexyl-4-aminopyrazolone l-n-decyl-4-aminopyrazolone l -phenyl-4-aminopyrazolone 1-( p-hydroxyphenyl )-4-aminopyrazolone 1-( p-sulfonylphenyl )-4-aminopyrazolone 3-methyl-4-aminopyrazolone 3-i-propyl-4-aminopyrazolone 3-n-octyl-4-aminopyrazolone 3-phenyl-4-aminopyrazolone 3-(p-ethylphenyl)-4-aminopyrazolone 3-( p-aminophenyl )-4-aminopyrazolone 3-( p-dimethylaminophenyl )-4aminopyrazolone 3-( m-chloroph'enyl )-4aminopyrazolone 3-(4-pyridyl)-4-aminopyrazolone lmethyl-3-phenyl-4-aminopyrazolone 1-ethyl-3-( o-hydroxyphenyl )-4-aminopyrazolone l-n-decyl-3-( p-metylaminophenyl )-4-aminopyrazolone I l-phenyl-3-n-butyl-4-aminopyrazolone l-( p-sulfonamidophenyl )-3-n-octyl-4-aminopyrazolone l-(p-sulfonarnidophenyl )-3phenyl-4aminopyrazolone l-( p-ethylphenyl )-3-phenyl-4-aminopyrazolone l-( p-betahydroxyethylphenyl )-3-phenyl-4- aminopyrazolone 1-( p-hydroxyphenyl )-3-n-octyl-4-aminopyrazolone l-( p-carboxyphenyl )-3-n-octyl-4-aminopyrazolone 1-( p-carb amidophenyl )-3-n-octyl-4-aminopyrazolone '4-aminopyrazolone-3-carboxylic acid 4-aminopyrazolone-3-carboxylic acid-ethyl ester 4-aminopyrazolone-3-carboxylic acid-n-butyl ester 4-aminopyrazolone-3-carboxylic acid-methylamide 4-aminopyrazolone-3-carboxylic acid-hydroxymethylamide 4-aminopyrazolone-3-carboxylic mide 4-aminopyrazolone-3-carboxylic hydroxyethylamide 1-methyl-4-aminopyrazolone-3-carboxylic' acid-ethyl ester 1 -methyl-4-aminopyrazolone-3-carboxylic propylamide l-methyl-4-aminopyrazolone-3-carboxylic acid-betahydroxypropylamide l-ethyl-4-aminopyrazolone-3-carboxylic acid-methyl ester l-ethyl-4-aminopyrazolone-3-carboxylic acid-amide acid-di-n-butylaacid-ethyl-betaacid-nethyl ester I l-n-heptyl-4-aminopyrazolone-3-carboxylic acid l-n-decyl-4raminopyrazolone-3-carboxylic acid-di-npropylamide g 1 -n-decyl-4-aminopyrazolone-3-carboxylic beta-hydroxyethyl ester l-phenyl-4-aminopyrazolone-3-carboxylic acid acid- 9 l-phenyl-4-aminopyrazolone-3-carboxylic acid-ethyl ester 1-phenyl-4-aminopyrazolone-3-carboxylic acid- [3- hydroxyethyl ester l-phenyl-4-aminopyrazolone-3-carboxylic acidamide l-phenyl-4-aminopyrazolone3-carboxylic acidethylamide 1-phenyl-4-aminopyrazolone-3-carboxylic acid-betahydroxyethyl-amide l -phenyl-4-aminopyrazolone-3-carboxylic aciddimethylamide l-( p-i-propylphenyl )-4-aminopyrazolone-3-carboxylic acid l-( p-hydroxyphenyl )-4-aminopyrazolone-3-carboxylic acid-ethyl ester 1 -(p-aminophenyl)-4-aminopyrazolone-3-carboxylic acid-amide 1 o-carboxyphenyl )-4-aminopyrazolone-3-carboxylic acid-ethyl ester 1-(p-sulfonylphenyl)-4-aminopyrazolone-3-carboxylic acid-ethyl ester l-(p-sulfonamidophenyl)-4-arninopyrazolone-3-carboxylic-acid-ethyl ester 1-( 2-pyridyl )-4-aminopyrazolone-3-carboxylic aciddiethylamide These compounds may be used as such or in the form of their water-soluble acid addition salts.

Suitable aromatic biand polyfunctional amines having at least one primary amino group and another functional group in para-position are, e.g., p-phenylened iamine, p-toluylenediamine, pdiaminoanisole, paminomethylaniline, p-aminoethylaniline, p-aminodiphenylamine, p-aminodimethylaniline, p-aminodiethylaniline, p-amino-di-beta-hydroxyethylaniline, paminophenyl, p-diamino-anisole, or compounds of the kind named which additionally contain one or more functional groups such as OH, Nl-l NHR, NRR", wherein R and R again are lower alkyls or hydroxyalkyls having 1 to 4 carbon atoms.

Preferably, these aromatic biand polyfunctional amines have the formula wherein Y is a member selected from the group consisting of OH, NH NHR', NR'R" and NHC H and Z is a member selected from the group consisting of H, R, Y and OR, where again R and R are alkyls or hydroxyalkyls having 1 to 4 carbon atoms. 1

These aromatic bior polyfunctional amines advantageously are employed in substantially equimolar amounts, calculated on the pyrazolones substituted in the 3-position. However, it is not disadvantageous to apply these pyrazolones in a given excess or in amounts slightly less than molar. Mixtures of the individual dyestuff components can be used.

Dyeing of the hair is carried out in aqueous media and, as customary for oxidation dyes, developed either by the action of atmospheric oxygen or by means of chemical oxidizers, preferably hydrogen peroxide or its adducts on urea, melamine, or sodium borate and mixtures of such hydrogen peroxide adducts with potasl0 sium peroxydisulfate. Effective temperatures are substantially 15 to 40 C, preferably room temperature.

The hair dyes of the invention can be present in the above named uses in the form of aqueous preparations, such as solutions or emulsions. Such solutions should contain the dyes or the dye combinations of couplingand developing components in amounts from 0.1 to 5%, particularly 2% by weight.

The compounds of the invention may also be applied in the form of creams or emulsions. To make such creams or emulsions, any desired surfactants may be employed, but especially anionic or non-ionic detergents or wetting agents. Suitable surfactants are particularly alkylbenzenesulfonates, higher fatty alcohol sul fates, high alkylsulfonates, higher fatty acid ethanolamides, ethylene oxide adducts on higher fatty acids, higher fatty alcohols or alkylphenols.

The dyeability of the materials named is not dimin ished in the presence of the surfactants or, in other words, when applied in cream form. Thus, the dyeing agents according to the invention can be manufactured in the form of shampoos, particularly cream shampoos, as frequently is desired in practice.

Moreover, other agents can be incorporated into the agents, such as thickeners in the form of methyl or by droxymethyl-cellulose, starch, higher fatty alcohols, Vaselineparaffin oils and higher fatty acids. Perfumes, i.e., essential oils, or hair grooming agents such as pantothenic acid and cholesterol, also may be incorporated.

Effective amounts of the additives names above are those customarily employed. Effective amounts for surfactants range from 0.5 to 30%, for thickeners from 0.1 to 25%, and the effective concentration of the dyestuffs or dyestuffs combination depending upon the use, range from 0.1% to 5% by weight, preferably 0.1% to 2% by weight. All those percentages are by weight and calculated on the total composition.

The hair dyes can be applied to the hair in weakly acid, neutral and preferably alkaline pH ranges at temperatures of from 15 to 40 C.

The dyeings attained are distinguished by good light and and fastness and fastness to rubbing. A new and unexpected advantage and a surprising property of the hair dye solutions and process, according to the invention, is that the hair dye solutions may be applied both as direct dyes and as coupling dyestuff agents in oxida tion dyes for the obtainment of yellow and blond hair dyeings.

The following examples are merely illustrative of the present invention without being deemed limitative in any manner thereof.

EXAMPLE I l-Amino-3-cyanoacetylamino-4-nitrobenzene 9.04 gm (0.059 mol) of l,3-diamino-4-nitrobenzene, 5.69 gm (0.054 mol) of cyanoacetyl chloride were boiled in ml of benzene for 4 hours at reflux. The precipitation of the reaction product occurred during the reaction and was completed by concentration of the reaction solution. The separated precipitate was purified by recrystallization from acetic acid. On the basis of the analysis data and IR- and NRM-measurements the product has the formula: l-arnino-3- cyanoacetylamino-4-nitro-benzene and a melting point of 21 8-220C.

point of 2 l 822 1C.

Analysis: C H N Analysis: (CQHHN4O3) C H N Calculated: 49.09% 3.66% 25.46% Calculated: 49.09% 3.64% 25.45% Found: 48.80% 3.63% 25.13% Found: 49.20% 3.48% 25.47%

- EXAMPLE X EXAMPLES u l-Amino-2-nitro-4-w-benzoylacetylamino-benzene 15.3 gm (0.1 mol) of l,4-diamino-2-nitrobenzene In an analogous manner, the compounds listed in Exwere suspended in 100 ml of xylol. This suspension wa amples 2 to 6 of the following table were obtained by heated- After the addition thereto 0f 8" reaction of l ,3-diamino-4-nitrobenzene with the folof ethyl benzoylacetate, i p n n s lowing named compounds, while in Example 7 the heated on an oil bath at 130 C with the simultaneous starting materials were 1-ac l i -3 i 4- i distillation of ethanol, formed in the reaction. The prebenzene d cyanoacetyl hl id cipitate was separated from the cold reaction mixture TABLE I Example Reaction- Reactions-Product Molar Ratio Analysis M.P.

No. Partner Calc Calculated "C C H N 2 Benzoyl- 3-Benzoylacetylamino- 1 l Calc. 60.20 4.38 14.04 219-221 acetic acid l-amino-4-nitrobenzene Found 60.19 4.55 14.03

ethyl ester 3 Cyanoacetyl- 1,3-Di(cyanoacetyl- 2 1 Calc. 50.18 3.16 24.38 223-226 chloride amino )4-nitrobenzcne Found 50.13 2.79 25.35 4 Malonic acid 1,3-Di-(m-ethoxycar- 2 l Calc. 50.39 5.02 1 1.01 94 96 mono-ethyl bonylacetylamino Found 50.46 4.30 10.94 ester chloride 4-nitrobenzene 5 Malonic acid 1-Amino-3-( arethoxy- (x) l l Calc. 49.43 4.90 15.73 172-173 mono-ethyl carbonyl-acetylamino) Found 48.43 4.61 15.83 ester chloride -4-nitrobenzene 6 Acetoacetic l-Amino-3-acetoacetyll 1 Calc. 50.65 4.67 17.71 139-140 acid ethyl amino-4-nitrobenzene Found 50.63 4.61 17.67

, ester 7 Cyanoacetyll-Acetylamino-3-cyano- I I 1 l Calc. 50.38 3.84 21.37 232-235 chloride acetylamino-4-nitro- Found 50.39 3.72 22.56

benzene (x) in the presence of an equimolar amount of triethylamine EXAMPLE VIII and processed, as described in Example I. The product had a melting point of l82*183C.

1 ,4-Dicyanoacetylamino-2-nitrobenzene 40 20.70 gm (0.2 mol) of cyanoacetyl chloride were dissolved in 370 ml of absolute benzene. 15.3 gm (0.1 AnalyS'S: C H N mol) of l,4-diamino-2-nitrobenzene were added to this Calculated: 60.20% 4.35% 14.05% solution, and the reaction mixture was heated for 6 Found: 59419? 14097 hours at boiling. After cooling, the precipitate formed was vacuum filtered, washed with ether and recrystallized from dilute acetic acid. The product has a melting EXAMPLE XI point of 23223 3C.

1 -Am1no-2-n1tro-4-( w-ethoxycarbonyl-acetylammo benzene A I 7.65 gm (0.05 mol) of l,4-diamino-2-nitrobenzene l C N were added to 80 m1 of absolute tetrahydrofuran and Calculated: 50.17% 3.14% 24.39% 5.1 (0.05 mol) of triethylamine at room temperature of Found: 49-99% 298% form a solution. While this mixture was being stirred, 7.5 gm (0.05 mol.) of malonic acid monoethylester chloride were added dropwise thereto. After termination of the addition, the mixture was stirred at room EXAMPLE IX temperature for another 6 hours. Then the solvent was "1 A i 2- i 4 l i evaporated in vacuo for the most part. The residue was 15.3 gm (0.1 mol) of 1,4-diamino-2-nitrobenzene uctioned off and recrystallized once from ethanol/acwere heated to boiling in ml of ethyl'cyanoacetate. tivated Charcoal and a Second time m at r- Th Simultaneously therewith the ethanol formed during ProduCt had a meltmg mt of 1330-1360(3- the reaction was removed by distillation. After the reaction mixture was cooled, the precipitate formed was vacuum filtered, washed with ether and recrystallized 65 Analyss' C H N from dilute acetic acid. The product had a melting Calculated: 49.44% 4.87% 15.73% Found: 49.99% 4.67% 15.38%

EXAMPLE X11 1 ,4-Bis-( m-ethoxycarbonyl-acetylamino )-2-.nitrobenzene 15.3 gm (0.1 mol) of 1,4-diamino-2-nitrobenzene were heated in 160 ml of absolute benzene together with 30.1 gm (0.2 mol) of malonic acid monoethylester chloride for 3 /2 hours at refluxing. After cooling the precipitate was suctioned off and recrystallized twice from isopropanol. The product had a melting point of 9697C.

Analysis: (C H N O C H N Calculated: 50.39% 4.99% l 1.02% Found: 49.94% 5.16% 1 1.06%

EXAMPLE XIII 1Amino-2-nitro-4-acetoacetylamino-benzene 15.3 gm (0.1 mol) of l,4-diamino-2-nitrobenzene 'were heated in 50 of chlorobenzene together with 20 Analysis: (C H, N C H N Calculated: 56.65% 4.67% 17.7 I Found: 56.65% 4.29% l7.73%

EXAMPLE XIV Into a cream emulsion of the following composition: parts by weight of fatty alcohols C C 10 parts by weight of fatty alcohol sulfate (technical mixture C C 75 parts by weight of water, were incorporated 2 parts by weight of l-amino-2-nitro-4-( mcyanoacetylamino)-benzene and the pH of the mixture adjusted to 9.5 by the addition of ammonia. Enough water was added to bring the emulsion up to 100 parts by weight total. The thusly obtained dye cream dyed natural- 1 6 greyed hair within 30 minutes to a buttercup yellow color. With dye creams of the same composition, which contained instead of the above named dye, the below listed compounds, the following hair colors could be obtained:

Dye Component Color Produced l,4-dicyanoacetylamino-2-nitrobenzene corn yellow l-amin0-2-nitr0-4-(w-benzoylacetylamino)- light yellow benzene 1-amino'2-nitr0-4(w-ethoxycarbonylyellow acetylamino)-benzene 1-amino-2-nitro-4-acetoacetylamino-benzene 1-amino-3-(areyanoacetylamino)-4-nitrobenzene l-amino-3(w-benzoylacetylamino)-4-nitr0- benzene 1-amino-3-(wethoxycarbonylacetylamino) 4- nitro-benzene l-amino-3-(aracetoacetylamino)-4-nitrobenzene 1-acetylamin0-3-(m-cyanoacetylamino)-4- nitrobenzene yellow-orange intensive maize mimosa yellow pale yellow primrose yellow greenish-yellow EXAMPLES XV to XIX 2% aqueous solutions of oxidation dye combinations were prepared from equimolar amounts of a coupling component taken from the examples listed below together with 4-amino-l-phenyl-3-carbamoyl-pyrazolone-5 as the developer component. The pH of each solution was adjusted to 9.5 by the addition of ammonia. Then after mixing each solution with the same volume of a 1% or of a 9% hydrogen peroxide solution, samples of natural greyed hair were treated with the dye solution. The treatment took place at room temperature (22 C). The colors produced by the hair dyeing solutions are summarized in the following Table 11.

0.01 mol of the below named coupling component and developer component. The pH of the emulsion was adjusted to 9.5 by the addition of ammonia. Enough water was added to bring the emulsion up to parts by weight total. Added to the emulsion was an equal volume of an oxidizing agent comprising a 1% or a 9% by weight solution of hydrogen peroxide. This mixture was applied to naturally grey hair for 30 minutes. The respective color produced from the various oxidation dyestuff combinations of coupler component and developer component are listed in Table III below.

TABLE III Example Dye Components Color No. Coupler Developer 1% R 0 9% H 0,

20 l-amino-3-cyan0acetyl- 2,5-diamino-anisole olive brown olive yellow amino-4-nitrobenzene 21 N,N-dimethylaminoaniline 22 p-toluylenediamine coffee brown coffee brown 23 l-phenyl-3-methyl canary yellow canary yellow 1 ,3,4-thiadiazolehydrazone-S 24 l-ethyl-pyridonemoss green moss green 2-hydrazone 25 l-acetylamino-fl'cyanop-toluylenediamine olive green honey yellow acetylamino4-nitrobenzene 26 l-benzoylacetylamino-Ii-amip-toluylenediamine olive brown olive yellow TABLE III-continued Example Dye Components Color No. Coupler Developer 1% H 9% H 0 no-4-nitrobenzene 27 l,3-di(w-ethoxycarbonylp-toluylenediamine grey brown grey brown acetylamino)-4-nitrobenzene 28 l-amino-B-(w-ethoxycarp-toluylenediamine grey. brown olive brown bonyl-acetylamino)-4- nitrobenzene I 29 N,N-dimethylaminodark green grey-green aniline I 30 4-amino-l-phenyl-3- golden yellow lemon yellow ethoxycarbonyl-pyrazolone-S 31 l-methyl-pyridone-2 grey-green grey-green* hydrazone EXAMPLES XXXlI L Into a cream emulsion of the following composition: 10 parts by weight of fatty alcohols of the chain length C C 10 parts by weight of fatty alcohol sulfate (Na salt) of the same chain length, and

adjusted to 9.5 by the addition of ammonia. Enough water was added to bring the emulsion up to 100 parts by weight total. Added to the emulsion wasan equal volume of a chemical oxidizing agent comprising a 1% or a 9% by weight solution of hydrogen peroxide. This mixture was applied to naturally grey hair for minutes. If instead of adding a hydrogen peroxide solution,

air were used as the oxidizing agent, the treatment time would be 30 minutes. The respective color produced TABLE IV from the various oxidation dyestuff combinations of coupler component and developer component are listed in the table below.

Example Dye Components a) developer b) coupling agent Shade of dyed hair l% H O solution 9% H 0 solution 4-aminol phenyl-3- carbamoyl-pyrazolone-5 p-toluylenediamine N-methyl-pyridone-2 -hydrazone 4-aminol -phenyl-3- carbamoyl-pyrazolone5 p-toluylenediamine N-methyl-pyridone-2 hydrazone 4-aminol -phenyl-3- carbamoyl-pyrazolone-5 4-aminol -phenyl-3- ethoxycarbonybpyrazolone 5 p-toluylenediamine N,N-dimethylamino aniline N-methyl-pyridone-2 -hydrazone 4-aminol -phenyl-3- N B-hydroxyethylcarbamoyl )-pyrazolone-5 4-amino-3-ethoxy-carbonyll -H-pyrazolone-5 4-aminol -plienyl-3- carbamoyl-pyraz0lone-5 p-toluylenediarnine N-methyl-pyridone-Z -hydrazone 4-aminol -phenyl-3- carbamoyl-pyrazolone-S p-toluylenediamine N-methyl-pyridone-2- hydrazone 4% H o -solution l-amino-2-nitro-4- cyanoacetylaminobenzene l ,4-bis-cyan0acetyl-amino-Z-nitrobenzene w-ethoxycarbonylacetylaminobenzene l-amino-2-nitro-4- wethoxycarbonylacetylaminobenzene l-amino-2-nitro-4- methoxycarbonyl-acetyl-amino-benzene l-amino-2-nitro-4- ethoxycarbonyl-acetylamino-benzene l -amino-2-nitro-4- acetoacetylaminobenzene l-aminO-2-nitrO-4- acetoacetylaminobenzene l-amino-2-nitro-4- benzoylacetylaminobenzene brown yellow banana yellow cream colored pompeian red apricot yellow mustard yellow apricot yellow apricot yellow ocher yellow ocher yellow clay yellow brass colored pompeian yellow golden yellow orange brown golden yellow caramel brown caramel brown olive yellow light brown brown light brown ocher yellow autumn-golden yellowish-brown brownish yellow golden yellow reddish golden dark brown yellow orange oak brown P p y" apricot yellow camel brown apricot brown bright brown orange cocoa brown brown madeira brown* ocher yellow deep yellow light brown yellowish brown light orange light brown Although the present invention has been disclosed in connection with a few preferred embodiments thereof,

variations and modifications may be resorted to by those skilled in the art without departing from the principles of the new invention. All of these variations and modifications are considered to be within the true spirit and scope of the present invention as disclosed in the foregoing description and defined by the appended claims.

I claim 1. An aqueous preparation for the direct dyeing of human hair consisting essentially of (1) from 0.1% to 5% by weight of a diamino-nitrobenzene compound of the formula selected from the group consisting of NHA',

and

in which X and X are each an electrophilic substituent selected from the group consisting of cyano, alkanoyl of 2 to carbon atoms, substituted alkanoyl of 2 to 10 carbon atoms with a substituent selected from the group consisting of nitro, phenyl, halo, cyano, carboxyl and sulfo, acyl of aromatic hydrocarbon carboxylic acids having 7 to carbon atoms, substituted acyl of aromatic hydrocarbon carboxylic acids having from 7 to 15 carbon atoms with a substituent selected from the grop consisting of lower alkyl, nitro, halo, cyano, carboxyl and sulfo, cycloalkylcarbonyl of 6 to 10 carbon atoms, alkoxycarbonyl of 2 to 10 carbon atoms, cycloalkoxycarbonyl of 6 to 10 carbon atoms, phenylalkoxycarbonyl of 8 to 16 carbon atoms, furoyl, and thenoyl; and A is a member selected from the group consisting of hydrogen, alkyl of 1 to 10 carbon atoms, hydroxyalkyl of l to 10 carbon atoms, N,N-dialkylaminoalkyl of 3 to 18 carbon atoms, alkanoyl of 2 to 10 carbon atoms, substituted alkanoyl of 2 to 10 carbon atoms, with a substituent selected from the group consisting of nitro, phenyl, halo, cyano, carboxyl and sulfo, acyl of aromatic hydrocarbon carboxylic acids having 7 to 15 carbon atoms, substituted acyl of aromatic hydrocarbon carboxylic acids having from 7 to 15 carbon atoms with a substituent selected from the group consisting of lower alkyl, nitro, halo, cyano, carboxyl and sulfo; and in which A is selected from the group consisting of A' and the activated methylene group -COCH -X, in which X has the same meaning as defined above with the proviso that whenever A is hydrogen, then X is not acetyl; (2) from 0% to by weight of a surfactant; (3) from 0% to 25% by weight of thickeners; and- (4) from 40% to 99.9% by weight of water.

2. The aqueous preparation for the dyeing of human lected from the group consisting of methylcellulose, hy-

, ,18 droxymethylcellulose, starch, higher fatty alcohol, vaselin, paraffin oils and fatty acids.

4. The aqueous preparation for the dyeing of human hair of claim 1,.in which said diaminomitrobenzene compound is selected from the group consisting of lamino-3-cyanoacetylamino-4-nitrobenzene, 3-benzoylacetylaminol -amino-4-nitrobenzene, l -amino-3 (w-ethoxycarbonyl-acetylamino )-4-nitrobenzene l amino-3-acetoacetylamino-4-nitrobenzene, l acetylamino-3-cyanoacetylamino-4-nitrobenzene, 1,4- dicyanoacetylamino-2-nitrobenzene, l-amino-Z-nitro- 4-w-cyanoacetylamino-benzene, l-amino-2-nitro-4-wbenzoylacetylamino-benzene, l-amino-2-nitro-4-( wethoxycarbonyl-acetylamino)-benzene, and l,4-bis-( wethoXycarbonyl-acetylamino)-2-nitrobenzene.

5. An aqueous preparation for the dyeing of human hair consisting essentially of (1) from 0.1% to 5% by weight of an oxidation dyestuffs combination of a developer component, and a coupling component in substantially equimolar amounts,

said coupling component consisting essentially of a diamino-nitro-benzene compound of the formula selected from the group consisting of in which X is an electrophilic substituent selected from the group consisting of cyano, alkanoyl of 2 to 10 carbon atoms, substituted alkanoyl of 2 to 10 carbon atoms with a substituent selected from the group con sisting of nitro, phenyl, halo, cyano, carboxyl and sulfo, acyl of aromatic hydrocarbon carboxylic acids having 7 to 15 carbon atoms, substituted acyl of aromatic hydrocarbon carboxylic acids having from 7 to 15 carbon atoms with a substituent selected from the group consisting of lower alkyl, nitro, halo, carboxyl and sulfo, cycloalkylcarbonyl of 6 to 10 carbon atoms, alkoxycarbonyl of 2 to 10 carbon atoms, cycloalkoxycarbonyl of 6 to 10 carbon atoms, phenylalkoxycarbonyl of 8 to 16 carbon atoms, furoyl, and thenoyl, and A is a member selected from the group consisting of hydrogen, alkyl of 1 to 10 carbon atoms, hydroxyalkyl of l to 10 carbon atoms, N,N-dialkyl-aminoalkyl of 3 to 18 carbon atoms, alkanoyl of 2 to 10 carbon atoms, substituted alkanoyl of 2 to 10 carbon atoms with a substituent selected from the group consisting of nitro, phenyl, halo, cyano, carboxyl and sulfo, acyl of aromatic hydrocarbon carboxylic acids having 7 to 15 carbon atoms, substituted acyl of aromatic hydrocarbon carboxylic acids having from 7 to 15 carbon atoms with a substituent selected from the group consisting of lower alkyl, nitro, halo, cyano, carboxyl and sulfo, and the activated methylene group CO-CH -X, in which X has the same meaning as defined above; said developer component is selected from the group consisting of (a) aromatic polyfunctional amines of the formula wherein Y is a member selected from the group consisting of.Ol-l, Nl-l NHR', NRR and NHC H and Z is a meter lselected from the group: consisting of H, R, Y and OR where R andR are members selected from the group consisting of alkyl and hydroxyalkyl'having l to 4 carbon atoms, (b) 4-aminopyrazolones of the formula wherein R is a member selected from the group consisting of hydrogen, phenyl, hydroxyphenyl, sulfonylphenyl, sulfonamidophenyl, aminophenyl, alkylolphenyl, alkylphenyl, alkylamino-phenyl, di-alkylaminophenyl, where the alkyls and alkylols have 1 to 4 carbon atoms, pyridyl, COOl-l, COOR', CONH CONHR' and CONRR where R and R" have the above defined meanings, and R is a member selected from the group consisting of hydrogen, phenyl, hydroxyphenyl, sulfonylphenyl, sulfonamidophenyl, aminophenyl, chlorophenyl, carboxyphenyl, carbamidophenyl, carbamidoalkylphenyl, carbamidodialkylphenyl, alkylolphenyl, alkylphenyl, alkylaminophenyl, dialkylaminophenyl, where the alkyls and alkylol have 1 to 4 carbon atoms, and pyridyl, and (c) water-soluble acid addition salts of said 4-aminopyrazolones; (2) from to 30% by weight of a surfactant; (3) from 0% to 25% by weight of thickeners; and (4) from 40% to 99.9% by weight of water.

6. The aqueous preparation for the dyeing of human hair of claim 5, wherein said solution has a further content of a chemical oxidizing agent. i 7. The aqueous preparation for the dyeing of human hair of claim 5, in which said diamino-nitrobenzene compound is selected from the group consisting of lamino-3-cyanoacetyl-amino-4-nitrobenzene, 3-benzoylacetylaminol-amino-4-nitro-benzene, 1 ,3-di- (cyanoacetylamino )-4-nitrobenzene, 1 ,3-di-(w-ethoxycarbonyl-acetylamino )-4-nitrobenzene, l-amino-3- (w-ethoxy-carbonyl-acetylamino)-4-nitrobenzene, lamino-3-acetoacetyl-amino-4-nitrobenzene, l acetylamino-3-cyanoacetylamino-4-nitro-benzene, 1,4- dicyanoacetylamino-2-nitrobenzene, l-amino-Z-nitro- 4-m-cyanoacetylaminc-benzene, l-amino-2-nitro-4-wbenzoyl-acetylamino-benzene, 1-amino-2-nitro-4-( wethoxycarbonyl-acetylamino )-benzene, l ,4-bis-( coethoxycarbonyl-acetylamino)-2-nitrobenzene, and lamino-2-nitro-4-acetoacetylamino-benzene.

8. A process for the direct dyeing of human hair consisting essentially of applying to said hair at temperatures ranging substantially from 15 to 40C for a time sufficient to affect dyeing, an effective amount of an aqueous preparation consisting essentially of 1) from 0.1% to 5% by weight of a diamino-nitro-benzene compound of the formula selected from the group consisting of in which X and X are each an electrophilic substituent selected from the group consisting of cyano, alkanoyl of 2 to 10 carbon atoms, substituted alkanoyl of 2 to 10 carbon atoms with a substituent selected from the group consisting of nitro, phenyl, halo, cyano, carboxyl and sulfo, acyl of aromatic hydrocarbon carboxylic acids having 7 to 15 carbon atoms, substituted acyl of aromatic hydrocarbon carboxylic acids having from 7 to 15 carbon atoms with a substituent selected from the group consisting of lower alkyl, nitro, halo, cyano, carboxyl and sulfo, cycloalkylcarbonyl of 6 to 10 carbon atoms, alkoxycarbonyl of 2 to 10 carbon atoms, cycloalkoxycarbonyl of 6 to 10 carbon atoms, phenylalkoxycarbonyl of 8 to 16 carbon atoms, furoyl, and thenoyl; and A' is a member selected from the group consisting of hydrogen, alkyl of l to 10 carbon atoms, hy-

droxyalkyl of 1 to 10 carbon atoms, N,N-dialkylaminoalkyl of 3 to 18 carbon atoms, alkanoyl of 2 to 10 carbon atoms, substituted alkanoyl of 2 to 10 carbon atoms with a substituent selected from the group consisting of nitro, phenyl, halo, cyano, carboxyl and su lfo, acyl of aromatic hydrocarbon carboxylic acids having 7 to 15 carbon atoms, substituted acyl of aromatic hydrocarboncarboxylic acids having from 7 to 15 carbon atoms with a substituent selected from the group consisting of lower alkyl, nitro, halo, cyano, carboxyl and sulfo; and in which A is selected from the group consisting of A and the activated methylene group COCH X, in which X has the same meaning as defined above; (2) from 0% to 30% by weight of surfactant; (3) from 0% to 25% by weight of thickeners; and 4) from 40% to 99.9% by weight of water.

9. The process for the dyeing of human hair of claim 8 in which said aqueous preparation contains from 0.5% to 30% by weight of a surfactant (2) selected from the group consisting of alkylbenzenesulfonates, fatty alcohol sulfates, alkylsulfonates, fatty acid ethanolamides and ethylene oxide adducts of fatty alcohols and alkylphenols.

'10. The process for the dyeing of human hair of claim 8 in which said aqueous preparation contains from 0.1% to 25% by weight of thickeners (3) selected from the group consisting of methylcellulose, hydroxymethylcellulose, starch, higher fatty alcohol, vaselin, paraffin oils and fatty acids.

1 1. A process for the dyeing of human hair consisting essentially of applying to said hair at temperatures ranging substantially from l5 to 40C for a time sufficient to affect dyeing, an effective amount of an aqueous preparation of claim 5.

12. The process for the dyeing of human hair of claim 1 1, wherein said preparation has a further content of a chemical oxidizing agent. 

1. AN QUEOUS PREPARATION FOR THE DIRECT DYING OF HUMANHAIR CONSISTING ESSENTIALLY OF (1) FROM 0.1% TO 5% BY WEIGHT OF A DIMAMINO-NITROBENZENE COMPOUND OF THE FORMULA SELECTED FROM THE GROUP CONSISTING OF
 2. The aqueous preparation for the dyeing of human hair of claim 1 in which said aqueous preparation contains from 0.5% to 30% by weight of a surfactant (2) selected from the group consisting of alkylbenzenesulfonates, fatty alcohol sulfates, alkylsulfonates, fatty acid ethanolamides and ethylene oxide adducts of fatty alcohols and alkylphenols.
 3. The aqueous preparation for the dyeing of human hair of claim 1 in which said aqueous preparation contains from 0.1% to 25% by weight of thickeners (3) selected from the group consisting of methylcellulose, hydroxymethylcellulose, starch, higher fatty alcohol, vaselin, paraffin oils and fatty acids.
 4. The aqueous preparation for the dyeing of human hair of claim 1, in which said diamino-nitrobenzene compound is selected from the group consisting of 1-amino-3-cyanoacetylamino-4-nitrobenzene, 3-benzoylacetylamino-1-amino-4-nitrobenzene, 1-amino-3-( omega -ethoxycarbonyl-acetylamino)-4-nitrobenzene, 1-amino-3-acetoacetylamino-4-nitrobenzene, 1-acetylamino-3-cyanoacetylamino-4-nitrobenzene, 1,4-dicyanoacetylamino-2-nitrobenzene, 1-amino-2-nitro-4- omega -cyanoacetylamino-benzene, 1-amino-2-nitro-4- omega -benzoylacetylamino-benzene, 1-amino-2-nitro-4-( omega -ethoxycarbonyl-acetylamino)-benzene, and 1,4-bis-( omega -ethoxycarbonyl-acetylamino)-2-nitrobenzene.
 5. AN AQUEOUS PREPARATION FOR THE DYEING OF HUMAN HAIR CONSISTING ESSENTIALLY OF (1) FROM 0.1% TO 5% BY WEIGHT OF A OXIDATION DYESTUFFS COMBINATION OF A DEVELOPER COMPONENT, AND A COULING COMPONENT IN SUBSTANTIALLY EQUIMOLAR AMOUNTS, SAID COUPLING COMPONENT CONSISTING ESSENTIALLY OF A DIAMNO-NITRO-BENZENE COMPOUND OF THE FORMULA SELECTED FROM THE GROUP CONSISTING OF
 6. The aqueous preparation for the dyeing of human hair of claim 5, wherein said solution has a further content of a chemical oxidizing agent.
 7. The aqueous preparation for the dyeing of human hair of claim 5, in which said diamino-nitrobenzene compound is selected from the group consisting of 1-amino-3-cyanoacetyl-amino-4-nitrobenzene, 3-benzoylacetylamino-1-amino-4-nitro-benzene, 1,3-di-(cyanoacetylamino)-4-nitrobenzene, 1,3-di-( omega -ethoxycarbonyl-acetylamino)-4-nitrobenzene, 1-amino-3-( omega -ethoxy-carbonyl-acetylamino)-4-nitrobenzene, 1-amino-3-acetoacetyl-amino-4-nitrobenzene, 1-acetylamino-3-cyanoacetylamino-4-nitro-benzene, 1,4-dicyanoacetylamino-2-nitrobenzene, 1-amino-2-nitro-4- omega -cyanoacetylamino-benzene, 1-amino-2-nitro-4- omega -benzoyl-acetylamino-benzene, 1-amino-2-nitro-4-( omega -ethoxycarbonyl-acetylamino)-benzene, 1,4-bis-( omega -ethoxycarbonyl-acetylamino)-2-nitrobenzene, and 1-amino-2-nitro-4-acetoacetylamino-benzene.
 8. A process for the direct dyeing of human hair consisting essentially of applying to said hair at temperatures ranging substantially from 15* to 40* C for a time sufficient to affect dyeing, an effective amount of an aqueous preparation consisting essentially of (1) from 0.1% to 5% by weight of a diamino-nitro-benzene compound of the formula selected from the group consisting of
 9. The process for the dyeing of human hair of claim 8 in which said aqueous preparation contains from 0.5% to 30% by weight of a surfactant (2) selected from the group consisting of alkylbenzenesulfonates, fatty alcohol sulfates, alkylsulfonates, fatty acid ethanolamides and ethylene oxide adducts of fatty alcohols and alkylphenols.
 10. The process for the dyeing of human hair of claim 8 in which said aqueous preparation contains from 0.1% to 25% by weight of thickeners (3) selected from the group consisting of methylcellulose, hydroxymethylcellulose, starch, higher fatty alcohol, vaselin, paraffin oils and fatty acids.
 11. A process for the dyeing of human hair consisting essentially of applying to said hair at temperatures ranging substantially from 15* to 40* C for a time sufficient to affect dyeing, an effective amount of an aqueous preparation of claim
 5. 12. The process for the dyeing of human hair of claim 11, wherein said preparation has a further content of a chemical oxidizing agent. 